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By Henry F. Hebley

This paper brings within the compass of one comparatively brief article a general description of the situation concerning the nation's water resources. It touches upon the phenomenal growth in the demand for water supply and emphasizes the problems facing the coal industry both with regard to acid mine water drainage discharged from active and abandoned mines and the suspended solids discharged to the stream system from wet coal preparation plants. IT must always be remembered, with regard to the problem of water-borne industrial wastes, that stream pollution from any cause is just one factor in the comprehensive problem of water supply in modern times. Industries nonexistent 25 years ago are now flourishing, and supplies of water piped to homes and apartments, as well as the greater number of plumbing fixtures per dwelling and per building, have created an ever growing demand on the country's water resources. Indication of this rapid growth in demand is shown in Table I, which is quoted from Abrams. of Texas increased 287% and the water consumption 7000 per cent." The domestic load varies greatly, depending on the extent of the available supply and the habits of the community. According to the report of the President's Water Resources Policy Commission' the United States Public Health Service reported a national average of 127 gal per capita per day, varying from 60 gal in communities of 500 persons to 140 or 150 gal in cities of 10,000 or over. Other critical areas may be cited to illustrate the inter-relation between new industrial processes and the demands for water in the area where the new enterprise is located. Powell and Wilson have pointed out that during World War 11, in the vicinity of Louisville, Ky., a rapid expansion of industry took place, consisting of numerous synthetic rubber plants. The demand for water increased from 37 million gal per day in 1937 to 62 million gal in 1943. These heavy requirements drew down the supply stored in the water-bearing aquifers to such an extent that urgent plans for recharging were considered. Similar situations have developed in the Los Angeles area and in the vicinity of Texas City. Warne4 has drawn attention to the situation in Los Angeles area, where in the West Basin the withdrawal of ground water in 1945 was 90,000 acre-ft, almost double the amount of the natural fresh water recharge. The draw down has been so severe that the level of the ground water is now below sea level, and sea water is invading the West Basin aquifers at rates up to 300 ft per year. In the Report of the Engineers Joint Council it is pointed out that in the area of Texas City the ground water table has been critically lowered. In 1930 the daily withdrawal from the water-bearing aquifer was 0.5 million gal. By 1945 the quantity withdrawn

Jan 1, 1954

By Carville E. Sparks, Rollin Farmin

TRIAL installations of rock bolts, of the slit-rod-and-wedge type, were under way at several units of Day Mines, Inc., when Korean hostilities interrupted the already slow deliveries of steel bars to the Coeur d'Alene district. Factory-made bolts had not yet been put on the local market, so the program was halted for lack of supplies. Interest was revived by a visitor's description of wooden roof bolts. These were said to have been used briefly with apparent success in a coal mine, until apprehension voiced by the U. S. Bureau of Mines caused the practice to be suspended. To make wooden bolts for trial in ground support, Day Mines acquired a second-hand doweling machine equipped with two cutting heads, one to turn out the desired round rods of 2-in. diam, the other to turn out 1-in. rods to be used as powder-tamping sticks. This machine was installed in the all-weather sawmill of the Hercules mine unit at Burke, Idaho, where fabrication of the wooden bolts commenced early in 1951. Most of the mining in the Coeur d'Alene district is along steeply dipping veins in shaly quartzite and argillite of Algonkian age. Ground support commonly is required in zones where the rocks have been sheared, brecciated, and hydrothermally altered. Pressure from the sidewalls is more troublesome than weight overhead, but both increase with the size of the mine opening. Caving may come from a progressive sloughing of irregular rock fragments or from an exfoliation and buckling of the layered wall rocks. The disintegration is thought to develop from an initial elastic expansion of the rock toward the newly-created mine opening, followed by the dilation of many tiny partings in the rock by absorption of water. As the partings widen, masses of rock develop weight and become free to fall. The function of rock bolts is to prevent or retard widening of partings in the rock supported. Wooden Bolts, Wedges and Headboards Bolt assembly used by Day Mines consists of a bolt 4 or 6 ft long, two wedges 16 in. long, and a headboard 30 in. long, Fig. 1. All four pieces are made of local red (Douglas) fir, either green or well-soaked in the mill pond before it enters the sawmill. Bolts are fabricated from cants, 2 1/4 in. sq, cut from relatively straight-grained timber with a minimum of knots and trimmed to 4- and 6-ft lengths. The bolt then is turned in the doweling machine from 21/4 in. sq to 2 in. diam round, except for a 4-in. length at one end which is left full square to provide the striking head and the shoulder that holds the headboard in position for wedging. The foot end of the bolt is slit with a thin saw for a length of about 16 in., thereby making a slot to receive the wedge against which the bolt is driven for anchorage at the bottom of the rock hole. A similar slit, 12 in. long, is made in the opposite (head) end of the bolt to receive the second wedge, which crowds the headboard against the ground at the collar of the rock hole and puts the bolt in tension. The second slot is aligned 90" from the plane of the first slot to avoid Longitudinal splitting and is notched out slightly to allow easier insertion of the collar wedge after the bolt has been driven to bottom. To prevent splitting the headboard by spreading action of the head wedge, this slot is oriented at 90" to the grain of the headboard when the pieces are assembled, Fig. 2. The wedges are similar to standard mine wedges, but more slender; they are cut 1 7/8 in. wide and 1 in. thick at the heel and taper out in 16 in. of length. The headboard, or bearing plate, is not necessary for some types of ground but generally is desirable because it helps the bolt to support an area of loose, friable rock and reduces the tendency for the rock at the collar of the hole to split away from the wedged head by distributing the pressure over a wider rock surface. The headboard may be a 24-to 30-in. length of 3-in. plank, 8 to 12 in. wide, but a similar length of rounded sawmill slab serves equally well at 20 pct of the cost. A hole of 2-in. diam is bored or punched through the center of the headboard, either at 90" or at various high angles to its surface. The bolt is inserted to its shoulder through this hole, then driven into the rock hole. Bolts, wedges, and headboards are given a full timber preservative treatment to inhibit rot. Bundles of each are immersed in a warm saturated solution of Osmose salts in water for 48 hr, removed, dripped dry, and stored in a relatively humid underground depot to cure. Most wooden rock bolts used by Day Mines are 4 ft long. Holes to receive them, about 42 in deep and 2 1/8 in. in diam, are drilled into the rock' to be supported, nearly normal to the periphery of the mine opening. The type of drill used is dictated by convenience: stoper, jackleg, or jumbo-mounted drifter. Correct depth of the hole is assured by use of a measuring stick that has been cut to the proper distance from drill chuck to the ground at the collar of the hole when a standard length drill rod is at the bottom. The bolt is seated to the shoulder through the hole in the headboard, the foot-end wedge is placed in its slot, and the assembly is inserted into the rock hole. Then the bolt is driven until it is seated solidly on the wedge against the bottom of the rock hole. Driving may be by hand with a sledge, or

Jan 1, 1954

By W. A. Cole

This report covers the preliminary phase of an investigation of some clays and shales and other materials in North and South Dakota to determine the feasibility of lightweight -aggregate manufacture in the two States. The background of the light - weight -aggregate industry, on a national basis, and results of preliminary laboratory testing of samples of North and South Dakota clays and shales from various localities are presented herein. The countrywide search for lightweight aggregates was necessitated toward the end of the 19th century by the change in building design from thick, heavy, load- bearing walls to a framework of structural steel .beams and columns with thin walls, followed shortly by the use of reinforced concrete and structural concrete as materials for the load-supporting frame. Ordinary concrete, with sand and gravel aggregate, weighs about 150 pounds to the cubic foot. A lighter concrete was needed to relieve the dead load and make it possible to construct higher buildings or add stories to existing buildings.

Jan 1, 1954

By M. J. Sinnott

WITH the advent of nodular iron as an engineering material, considerable interest has been shown in developing this material for various applications. Generally the strength, hardness, or ductility are the more common properties used for design purposes but occasionally applications involving a knowledge of the thermal conductivity of the material is required. A search of the literature showed, rather surprisingly, that relatively little work has been done on this property for all types of cast iron. Insufficient data are available on thermal and electrical conductivities to develop the Weidemann-Franz ratio, or the Lorentz relationship, for estimation purposes. There are no data on nodular irons and the published data on malleable irons are quite sketchy. For these reasons the conductivity of the group of nodular irons listed in Table I were measured. Irons I to IV were made in such a fashion as to maintain the carbon and alloy content essentially the same while varying the silicon content. Test specimens were cut from the mid-section of 4-in. keel castings. Iron V is a commercial casting of nodular iron. The test specimen of this iron was cut from the center of a large cast billet 3x10x26 in. All alloys were tested in the as-cast condition. A microstructural examination showed that each iron had spheroidal graphite but the size and distribution varied with the silicon content of the iron. The spheroid size decreased while the number of graphite nodules increased as the silicon content of the iron was increased. The matrix structures of each iron consisted of pearlite and ferrite with the proportions varying from predominantly pearlite in the low-silicon iron to mostly ferrite in the high-silicon iron. The commercial heat, iron V, was predominantly pearlite probably because of its higher manganese and phosphorus content. Two methods for measuring the thermal conductivity were used. The first was a modification of the techniques described by Powell and Hickman and Van Dusen and Shelton,² the second method was a simpler technique described by Jakob and Hawkins." Since the agreement of both methods as tested on two sets of duplicate samples was excellent, the simpler experimental technique was used. The results of the measurements are given in Table II along with a summary of the microstructural constituents. These conductivity data indicate that as the percentage of silicon increases there is a corresponding decrease in the thermal conductivity even though the structure is changing from pearlitic to ferritic. Such a change in microstructure is usually accompanied by an increase in conductivity. A third factor involved in the behavior of these irons is the size and distribution of the graphite nodules. The relative amounts of graphite do not change greatly but the size and distribution do. Generally graphite improves the conductivity but in the present case such an effect is probably masked by the alloying effect from the silicon and its dispersion through the matrix. The thermal conductivity of the nodular irons studied is less than that of regular foundry irons by some 10 to 30 pct and is less than that of regular malleable irons.' The cause of the decreased conductivity is probably the more highly alloyed fer-rites obtained in these irons and the changed mode of distribution of the graphite as compared to the regular foundry irons. References R. W. Powell and M. J. Hickman: Journal Iron and Steel Inst. (1946) 154, No. 2, p. 99. 'M. S. Van Dusen and S. M. Shelton: U. S. Bur. Standards Journal of Research, RP668 (1934) 12, p. 429. ³M. Jakob and G. A. Hawkins: Elements of Heat Transfer and Insulation. 2nd Ed. (1950) New York. John Wiley and Sons. ' J. W. Donaldson: Journal Iron and Steel Inst. (1933) 128, No. 2, p. 255.

Jan 1, 1954

By R. K. McGeary, B. Lustman

Orientation relationships and rates of annealing of 97 pct cold rolled zirconium have been studied by X-ray techniques, metallography, and by hardness measurements. The process of annealing occurring by the formation of domains, and their subsequent growth without recrystallization, is demonstrated. NUMEROUS investigators1-' have revealed sub-grain formation after annealing cold worked metal single crystals and have generally described the results in terms of a dislocation mechanism of polygonization.5,6 in heavily cold rolled polycrystal-line aluminum the first stages of heating cause an apparently spontaneous subdivision of regions of the deformed matrix into a great number of slightly disoriented domains followed or accompanied by rapid growth of certain domains to form a recrystallization texture.7,8 In the present investigation the isothermal rate of annealing of cold worked polycrystalline zirconium has been studied by X-ray techniques, metallography, and by hardness measurement. It will be shown that, rather than by the usual nucleation and growth mechanism,"12 the process of annealing can best be explained by the formation of domains early in the annealing treatment and the subsequent growth of these domains without recrystallization. Experimental Procedure All the experimental work was performed on an arc-melted ingot of high purity zirconium crystal bar made by Westinghouse in a production scale deBoer unit. The weight percentage of impurities in the zirconium were as follows: C, 0.04; Fe, 0.05; Hf, 0.014; W, 0.01; Ti, Ni, and Al, 0.003; Si and N, 0.002; Cr and Cu, 0.001. Metallographically the zirconium showed only a single phase. The 4 in. diarn ingot was forged at 760°C to a 1 1/2x3 in. plate and was then rolled at 760°C to 0.150 in. thickness and annealed at this temperature for 20 min to produce an equiaxed grain structure of about 0.1 mm average grain diameter. The hot rolled plate was roller-leveled, surface ground to 0.135 in., cold rolled 83 pct reduction in thickness on a two-high mill, and then to a total reduction of 97 pct on a Sendzimir mill. The 0.004 in. strip material so produced received no subsequent mechanical treatment. Specimens % in. square were sheared from the rolled strip and isothermally annealed at 104 mm Hg in an all glass vacuum system equipped with a Vycor furnace tube. The temperature data presented are the average temperatures during the runs and did not vary more than about k3"C. X-ray Diffraction Methods: When zirconium is drastically cold rolled, a high degree of preferred orientation results in which prism poles, {1010}, are perpendicular to the rolling direction. After fully annealing this material an entirely new texture develops which corresponds to a 20" or 40" rotation of the deformation texture about hexagonal axes of

Jan 1, 1954

By O. C. Blade

This report on the properties of aviation gasolines and aviation jet fuels produced in the United States during 1953 was made under a co-operative agreement between the American Petroleum Institute and the Bureau of Mines of the United States Department of the Interior. Analytical data are presented for 101 samples of aviation gasoline which include, for the second time in this series of reports, data on some samples of grade 108/135 aviation fuel. Data also are given for 32 samples of aviation jet fuel. The analyses were made on samples typical of the manufacturers' production in their laboratories and the results sub-mitted to the Bureau of Mines for compilation. The products of 19 manufacturers of aviation gasolines and of 19 producers of aviation jet fuels are represented.

Jan 1, 1954

By E. B. Fitch, E. C. Johnson

The operating behavior of liquid-solid cyclones is outlined, together with the nature and range of the process results obtainable, to serve as a background for engineers wishing to consider application of this new process tool. BY now most engineers are familiar with the liquid-solid or Dutch State Mines cyclone. However, it should be helpful to know exactly what it is that the equipment does and what its limits are. Without going into cyclone theory, this paper will describe the operating characteristics of Dutch State Mines cyclones. These are manufactured under license in this country and sold under the trade-marked name of DorrClone. The physical construction of the liquid-solid cyclone has been covered in many papers,'-' the DorrClone in particular being described in some detail by Weems. Fig. 1 shows the unit in cross-section. The feed enters at C. The coarse, heavy particles are thrown centrifugally to the periphery and make their way down the wall to the apex where their rate of discharge as underflow is controlled by an adjustable rubber apex valve. As the apex diameter is decreased the solids build up behind the valve, producing a denser underflow. Meanwhile the fine particles are swept into the upward flowing vortex stream which exits as overflow through the vortex finder, F. Flexibility to produce the specific result desired in a particular process is achieved by providing means for varying the areas of the entrance, vortex discharge, and apex discharge. The entrance area may be varied by insertion of special shims. Vortex discharge area may be changed by use of different-sized vortex finders which are interchangeable. Similarly, the different sizes of apex valves are interchangeable and in addition each apex valve is variable down to about 60 pct of its maximum diameter. A most significant primary distinction to make is that although liquid-solid cyclones have been sometimes called thickeners, they actually are classifiers, and very potent ones. They are almost never thickeners in the special sense that many metallurgical engineers understand the term. There would be no profit in quibbling over the definition of a word, but when the application of cyclones is considered, it will help to understand the difference be- tween two mechanisms, one of which will be called classification, and the other thickening. In what is called thickening the fine solid particles present in the feed hold together by surface attraction during the sedimentation process. The loose network of particles thus held together constrains all particles to settle at approximately the same rate, the larger ones dragging the smaller ones down. As a result, pulp settles with a sharp line of demarcation between solids and a relatively clear supernatant liquid. Essentially all the solids, regardless of their fineness, pass into the thickened underflow, and a clear overflow is separated. In classification, on the other hand, the interparti-cle forces are relatively insignificant as compared to the settling force on the individual particles, and are insufficient to prevent independent movement of the particles. The coarsest, heaviest particles settle most rapidly through the pulp, passing more slowly settling fines. Particles coarser than the mesh-of-separation essentially all settle into the underflow, but if the feed contains any particles finer than the mesh of separation, at least part of them will appear in the overflow. A clear supernatant or overflow can be obtained only if there are no undersize particles present in the feed. Thus it will be seen that classification is impossible under ideal thickening conditions. The finer particles are pulled down at essentially the same rate as coarser particles, and there is no separation on the basis of particle size. The surface attraction holding the particles together in a thickener is usually feeble. Whenever the sedimentation force on any particle is strong with respect to the interparticle forces, that particle can pass through the tenuous structure and settle independently. There are at least four ways of making the sedimentation force strong, with respect to the interparticle forces, and obtaining classification. First, and most obvious, the particles may be large and heavy. Thus coarse sands settle out in a beaker or Dorr thickener ahead of the rest of the thickening solids. Second, the interparticle forces may be altered by physicochemical means; i.e., it is often necessary to add dispersing agents to destroy the interparticle forces and permit classification to take place. Third, the interparticle forces may be reduced by dilution of pulp. It is well known that to obtain the most efficient separation of

Jan 1, 1954

By G. F. Carr

"IntroductionFLUORSPAR has been found at several •localities in Newfoundland, but all the commercial deposits discovered to date are in the vicinity of St. Lawrence, a town on the southeast coast. Most of the veins are within six miles of St. Lawrence harbour, and between sea-level and an altitude of 400 feet. The St. Lawrence Corporation of Newfoundland, Limited, and Newfoundland Fluorspar, Limited, a subsidiary of the Aluminum Company of Canada. Limited. are the two producers.With the arrival of 1953, the St. Lawrence area entered upon its twenty-second •consecutive year as a producer of fluorspar. Production has increased more or less steadily during this period, as is shown by the fact that approximately one-half of the total shipments to date have been made during the past six years. Between four and five hundred men are employed by the industry, and more than $1,250,000 was paid out in wages and salaries during 1952. Shipments during that year reached an all-time high of 81,283 tons valued at $2,484,943, compared with 67,925 tons valued at $1,966,477 in 1951 (1).As a result of an agreement made in July, 1952, with the United States Defence Materials Procurement Agency, production of the St. Lawrence Corporation, Limited, and St. Lawrence Fluorspar, Incorporated, an affiliated company, will •be increased by .approximately 50,000 tons of acid-grade fluorspar per year. The contract extends over a period of four years, or until 150,000 tons of acid-grade concentrates have been produced."

Jan 1, 1954

By C. D. Starr

IT is well known that the martensite reaction can be induced to occur isothermally above the M, temperature by plastic deformation of an alloy in its austenitic state, and also that as the test temperature is increased above the M. temperature, plastic deformation under a given set of conditions merely causes additional slip with a corresponding tendency toward the formation of less martensite per unit of strain. Thus it appears that a maximum temperature exists above which martensite cannot be formed isothermally by plastic deformation. This temperature is commonly designated as the equilibrium temperature Te. Attempts to determine experimentally the equilibrium temperature have indicated that a critical temperature is observed, under a given set of conditions, above which martensite cannot be formed isothermally by plastic deformation. But the observation of a "so called" critical temperature, Te, should not be confused with the equilibrium temperature, Te. In order to clarify this anomaly, true stress-strain curves were obtained for a series of type 304 stainless steel specimens (manufacturer's analysis, 0.08 pct C, 18 to 20 pct Cr, 8 to 10 pct Ni, balance Fe) over the temperature range 67" to 300°K.' Since martensite is magnetic, a quantitative measure of the amount of martensite that was produced by plastic deformation was obtained by determining the magnetic permeability as a function of strain. The results of these tests are given in Fig. 1. They appear to indicate that a plastic critical point does exist at about 240°K for the stainless steel under investigation here. But that 240 °K is not the equilibrium temperature nor even a true plastic critical temperature can be seen from Fig. 2 wherein the permeability of the same material is shown to increase with cold rolling at 293 OK. Consequently the observation of a "so called" plastic critical temperature is dependent on the mode of deformation and has no theoretical significance. Acknowledgment This work was sponsored by the Office of Naval Research. Permission to publish this note is gratefully acknowledged.

Jan 1, 1954

By R. W. Stahl

One of the broad purposes of the Bureau of' Mines since its establishment has been conservation of mineral resources. As some of the coal beds approach depletion, especially those coals suitable for making metallurgical coke, more and more attention is being given to means of recovering a larger percentage of coal in place. The customary system of mining in the United States is by room and pillar, or some variation thereof, which leaves pillars of coal to support, the roof. In many operations, where the pillars are not systematically recovered, the loss of coal often amounts to 50 percent or more of the original deposit. In many instances in developing new mines, It is planned to recover chain and barrier pillars on retreat when the mine has reached established boundaries. Too often, however, mines are abandoned for some unforeseen reason before completion of mining without recovering any pillars. Usually, these pillars are lost forever. With this in mind, the Mining Division, Region VIII, of the Bureau; of Mines is encouraging mining by longwall methods. It is a generally known fact that almost all of the European coal is mined by longwall methods, which are conducive to a high percentage recovery of coal. A comparison between mining systems usually is on the basis of tons per man per shift. Unless all operating conditions are similar, such a comparison could be misleading. Generally, the output per man shift in European longwall mines is less than that obtained in room-and-pillar mining in the United States. In European mining, maximum recovery of coal is not only mandatory but it must be accomplished without major damage to surface by subsidence. These restrictions necessitate packing or stowing with consequential increases In manpower and decreases in output per man shift.

Jan 1, 1954

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By H. L. Gilbert, H. A. Johansen, R. G. Nelson

High purity electrolytic chromium plate has been hydrogen-reduced and arc-melted under inert atmosphere to give sound ingots. These ingots may be hot forged to break the as-cast structure and then worked at 500°C to finished form. An intermediate and final high temperature anneal gives best ductility and grain refinement. HE increasing interest in refractory metals for I use in high temperature gas turbines, jets, and rockets has led to great efforts in exploiting the fifth and sixth groups of transition elements. Much of the interest has centered upon production of metals that can be worked and fabricated by normal means to produce various engine parts or components having the high temperature characteristics of oxidation resistance and high creep strength required for such uses. If these pure elements do not exhibit all of the desired characteristics, it may be possible to obtain a high purity alloy that will. Since, in all cases, development of these transition elements has depended to a large extent upon removal of oxygen and nitrogen as a means for producing ductile metal, the hypothesis has been accepted that oxygen is the normal embrittling material in a high grade electrolytic chromium metal. Various methods have been employed in an effort to remove this oxygen by direct or indirect attack.' Many workers have endeavored to produce pure chromium through reduction of the oxide by carbon or active metals, while others have recommended fusion electrolysis of chromium salts or reduction of these salts by active metals, such as sodium or calcium. Hydrogen reduction of the oxide or chloride and thermal dissociation of the iodide have been reported to give high purity metal. Experimental Work The U. S. Bureau of Mines, Northwest Electro-development Laboratory, has systematically re-examined the more promising methods and developed two which produce metal having ductility at temperatures lower than heretofore described. It has been found' that oxide-free chromium chlorides in a NaCl-KCl carrier salt may be mag- nesium-reduced and the byproduct salts distilled off in vacuo to give a high purity chromium sponge. Fusion analysis conducted under the supervision of W. W. Horton of Knolls Atomic Power Laboratory showed the oxygen and nitrogen both to be below 10 parts per million on a selected sample. A small amount of carbon is carried over in the final metal from the chlorination and reduction steps which are carried out in graphite crucibles. This trace of carbon is not detrimental to hot ductility. A more practical method for producing ductile metal is through hydrogen reduction of high purity electrolytic chromium. Normal electrolytic chromium will, if "developed" for a few minutes at 1100°C in high vacuum, be found by the method of Adcock:; to contain about 1 pct chromium sesquioxide (Cr2O3). This small amount of oxygen may be effectively reduced by hydrogen.2, 4 The method employed was to crush electrolytic chromium plate in a gyratory crusher to pass 60-mesh; finer crushing appears to offer no advantage. A nitric acid leach removed the iron picked up during crushing. The leached powder was rinsed until neutral with distilled water and vacuum-dried.

Jan 1, 1954

By R. F. Domagala, M. Hansen, D. J. McPherson

On the basis of metallographic analysis, incipient melting data, thermal analysis work, and X-ray diffraction, phase relationships in the 0 to 50 atomic pct Cr region were carefully resolved. Phase relationships in the 50 to 100 atomic pct region were outlined. A single intermediate phase, ZrCr,, was established in the system. A eutectic and a eutectoid were found in the zirconium-rich region of the system, while a eutectic was located in the chromium-rich region. Limited solubility of chromium in both a and a zirconium was observed. THIS is another in a series of papers on zirconium-base binary phase diagrams based on a program sponsored by the Atomic Energy Commission. The Zr-Sn,' Zr-Si,' and Zr-Mo and Zr-W" systems have already been published. Previous work on the Zr-Cr system includes a partial diagram by Hayes, Roberson, and Davies' and a complete diagram by McQuillan." The phase relationships reported by these authors were determined with magnesium-reduced zirconium, whereas those reported herein are based on iodide metal. Some X-ray work on the intermediate phase in this system was also reported by Hayes et al., as well as by Wallbaum.' Comparisons with these data are made in the appropriate sections. Thermal analysis, metallographic and incipient melting techniques were employed to accurately resolve phase relationships in the 0 to 50 atomic pct Cr region, while the remainder of the diagram is outlined on a basis of cast structures and thermal analysis. A description and analyses of the metals used in the preparation of alloys for this study are included in Table I. A "low-hafnium" zirconium crystal bar (Westinghouse "Grade 3") was used. This material was produced by the decomposition of a volatile iodide onto a hot zirconium filament. The as-received crystal bar was coated with corrosion product from a standard autoclave test by which its grade designation is determined. A sand-blasting and subsequent HF-HNO, pickling treatment was employed to remove this contamination. The bars were cold-rolled to approximately 1/32-in. sheet, pickled again, sheared to 1/4-in. squares, washed with acetone, and stored for use. Ingot chromium metal from National Research Corp. and electrolytic chromium flakes from Johnson, Matthey and Co., Ltd., were available as alloy additions. The ingot chromium was received in granular form. The large granules were sized by crushing, treated for iron removal, rinsed with acetone, and stored. The flakes were broken to approximately 1/8 in. with mortar and pestle, cleaned with acetone, and stored for charging. Experimental Procedure A nonconsumable electrode arc furnace identical to that described by Hansen, Kessler, and McPher-son,' was used in this work. A 400 amp dc welding generator was the source of power. To insure homogeneity, ingots were melted in a water-cooled spun copper crucible, a total of four times without opening the furnace. No difficulties were encountered in the preparation of these binary alloys. Analyzed chromium contents were found to agree very well with the intended content. Melts of pure zirconium were interspersed in the course of preparing the alloys and their hardness was measured to keep a constant check on the melting technique. Vycor and quartz bulbs were used to contain the samples for isothermal annealing treatments. Vycor bulbs were employed for temperatures up to 110O°C, while quartz was used above this temperature. For treatments up to 950°C the bulbs were evacuated before sealing, but for higher temperatures a partial pressure of argon was admitted to the

Jan 1, 1954

By F. J. Alcock

The Appalachian region of Canada comprises the three maritime provinces; Nova Scotia; New Brunswick; and Prince Edward Island; and that; part of the Province of Quebec lying south and east of Logan's fault. This; major thrust runs in a gently curving line from lake Champlain to Quebec; city and thence down the valley of the St. Lawrence to pass between Anticosti; island and Gaspe peninsula. To the northwest lies the St. Lawrence; Lowland division of the Interior Plains geological province; a region underlain; largely by early Palxozoic strata; which for the most part lie horizontal; or with low dips; where faults occur they are predominantly of the normal; type; and only locally are the beds cut by intrusive rocks. To the southeast; on the other side of the fault zone; an entirely different set of conditions is; encountered. There; Lower Devonian and older strata stand at high angles; are sheared and thrust faulted; and are intruded in many places by granitic; igneous bodies. The present paper is designed to outline briefly the geological; and structural history of this geological province and to emphasize; the part that structural conditions have played in connection with mineral; deposition.

Jan 1, 1954

By J. Chipman, N. J. Grant, B. M. Shields

The vacuum tin-fusion method of analysis for hydrogen, developed by Carney, Chipman, and Grant, has been modified to permit the analysis of the evolved gases for hydrogen by means of a thermal conductivity cell. A properly prepared sample can be analyzed in 10 min with a probable error of ±0.12 ppm. A study of various methods for storage of hydrogen samples shows that samples can be safely held in a dry ice-acetone bath as long as six days. Storage in liquid nitrogen is necessary for samples to be held one week or more. HE vacuum tin-fusion method, as developed by I- Carney, Chipman and Grant,' is the only analytical procedure which has shown promise of being fast enough for use in the control of hydrogen during steelmaking. It was felt that further simplification and faster speed of operation could be effected by the use of thermal conductivity measurements for analysis of the gases evolved in the tin-fusion method. The application of conductivity measurements to the tin-fusion method is possible because: 1—the evolved gas is essentially a mixture of hydrogen, nitrogen and carbon monoxide with a hydrogen content usually over 50 pct, 2—the evolved gas is collected at a relatively low pressure, and 3— the thermal conductivities of CO and N2 are practically identical while that of hydrogen is very much greater. The major part of this research program was devoted to the construction and calibration of a vacuum tin-fusion apparatus which analyzes the evolved gases for hydrogen by means of a thermal conductivity cell. The second phase of the problem was associated with the development of a procedure for storage of samples prior to analysis. With the rapid quenching method for hydrogen sampling,' which seems to be the most practical for steel mill use, it is necessary that the samples be stored safely during the interval between sampling and analysis if the hydrogen content of the molten metal is to be maintained in the supersaturated solid samples. The thermal conductivity bridge has been used for a number of years in the analysis of certain gas mixtures. An elementary discussion of the theory and practice of gas analysis by thermal conductivity measurements is given by Minter.3 A more comprehensive discussion of the theory and of the various measuring circuits is presented by Daynes.' A complete knowledge of the theory and properties of the thermal conductivity of gases and gaseous mixtures can be gained by a study of the standard textbooks on the kinetic theory of gases."' The existing data on the thermal conductivity of single gases are reviewed by Hawkins: that for a number of binary gas mixtures by Daynes' and Lindsay." The thermal conductivity method may be applied to the determination of the composition of a binary mixture if: 1—the thermal conductivity of the mixture varies monotonically with composition, and 2— the two gases have measurably different thermal conductivities. The greater the difference between the two gases, the greater the sensitivity of the method.10 he method is applicable to the analysis of multicomponent mixtures when all of the gases in the mixture except one have nearly the same thermal conductivity. Fortunately, the mixture of hydrogen, nitrogen, and carbon monoxide evolved by the tin-fusion analysis' falls in this latter classification. The thermal conductivities of nitrogen and carbon monoxide are practically equal; and the thermal conductivity of hydrogen is approximately seven times that of the other two. Therefore, the thermal conductivity of a gaseous mixture of hydrogen, nitrogen, and carbon monoxide at known temperature and pressure can be related directly to the percentage of hydrogen in the mixture by suitable calibration. Usually the thermal conductivity of a mixture of gases is measured at atmospheric pressure where the thermal conductivity is independent of pressure over a wide pressure range. At very low pressures (below 1 mm Hg), the thermal conductivity of gases varies with the pressure. This phenomenon has been utilized in the Pirani vacuum gage for the measurement of pressures in the range of 10" to 10-0 mm of mercury.= Very little has been published concerning the variation of thermal conductivity with pressure at intermediate pressures between 1 mm Hg and 1 atm. However, preliminary measurements indicated that the thermal conductivities did vary with pressure over the range of pressures (up to 10 mm Hg) at which gases are delivered from the vacuum pump. Therefore, the calibration of the thermal conductivity cell had to be planned to include the effects of both gas composition and pressure. Such a calibration chart is shown in Fig. 4. Most industrial applications of the thermal conductivity method of gas analysis have used a compensated Wheatstone bridge circuit containing two

Jan 1, 1954

By Joseph J. Wallace

1. The investigation shows that there are two coal beds of major importance in Perry County from the standpoint of present production -Flag and Fire Clay -and two beds of minor importance -Haddix and Hindman. The Flag and Fire Clay beds contain the largest remaining known reserves. 2. Known measured and indicated reserves in all beds, based on a minimum thickness of 14 inches and 1,800 tons per acre-foot of coal in place, are estimated at 840 million short tons as of January 1, 1954. Of this total, 720 million short tons is in beds 28 inches and more thick. Areas in each bed were omitted from the estimate because available data relative to the bed characteristics are too meager for making an estimate that conforms with the definitions of measured and indicated coal adopted for this study. Should future drilling or development prove reserves in these areas, these should be added to the total estimated reserves.

Jan 1, 1954

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By O. C. Blade

This report on the properties of motor fuels sold through service stations in the United States was made in accordance with a cooperative agreement between the American Petroleum Institute and the Bureau of Mines of the United States Department of the Interior. By agreement with the American Petroleum Institute, identification of the items is confidential. It presents analytical data for 4,680 samples, representing the products of 130 companies. The samples were collected during December 1953 and January and February 1954. As in previous surveys, the gasolines covered by this survey include those from both large and small suppliers. The data were obtained by laboratories of various refiners, motor manufacturers, and chemical companies and submitted to the Bureau of Mines for compilation. A list of the National Motor-Gasoline Survey reports published during the past ten years is given on page 5.

Jan 1, 1954

By R. T. C. Rasmussen, L. H. Banning, W. E. Anable

In the rapidly growing industry of elemental-phosphorus production from western phosphates, most of the vanadium and chromium contained in the phosphate rock collect in the byproduct ferro-phosphorus. Results are presented of a completed laboratory project, which developed a tristage crystallization and hydrolysis process for recovering strategic vanadium and chromium, as well as a valuable phosphorus product, after extracting these elements from the ferro-phosphorus by roasting and leaching. THE Phosphoria formation in Idaho, Montana, Wyoming, and Utah contains the Nation's largest reserve of phosphate rock. A unique feature of the Phosphoria beds is their content of a fraction of a percentage each of vanadium, chromium, nickel, and molybdenum. Vanadium is the most important as to quantity and value. Small-scale tests by the Bureau of Mines at Albany, Oregon, in 1947, indicated that most of the vanadium in the phosphate rock collects in the ferrophosphorus product of smelting. Subsequent electric smelting operations to produce elemental phosphorus from western phosphate rock (experimentally by TVA and industrially at Pocatello, Idaho) have shown that the vanadium and other metals in the rock are to a large extent recovered in concentrated form in the ferrophosphorus byproduct. This paper reports the results of completed laboratory research on the recovery of vanadium from ferrophosphorus, which was undertaken by the Bureau of Mines at Albany in 1948 as the first phase of a project entitled, "Vanadium and Fluorine from Western Phosphates." The various vanadium-recovery methods investigated, including the roast-leach method that showed most promise and was studied in greatest detail, are discussed in an earlier publication.' Subsequent systematic study of the roast-leach method of extracting vanadium from western ferrophosphorus developed the more effi- cient tristage crystallization process, which is the subject of this paper. Process Development The investigations were made on ferrophosphorus produced in the electric smelting of elemental phosphorus from western phosphate rock. The TVA provided two sample lots of ferrophosphorus produced in pilot plant smelting of phosphatic shale from the Fort Hall Indian Reservation in Idaho. The Westvaco Chemical Div. of the Food Machinery & Chemical Corp. supplied two sample lots of ferrophosphorus produced by its phosphorus smelter at Pocatello, Idaho. The analyses of all four lots are shown in Table I. Westvaco lot B was the starting material for the more recent tests. The roast-leach process for recovering vanadium from western ferrophosphorus, as originally developed, employed the following principal steps: Roasting of a mixture of pulverized ferrophosphorus, soda ash, and salt; extraction of the water-soluble vanadium, phosphorus, and chromium compounds from the calcine by leaching, settling, and decanta-tion of the pregnant solution; primary crystallization of trisodium phosphate from the pregnant solution; purification of the trisodium phosphate crystals by dissolution in water and secondary crystallization; purification of the pregnant vanadium solution from the primary crystallization step by adding calcium chloride to precipitate calcium phosphate; and hydrolysis of vanadium red cake from the puri-

Jan 1, 1954

By L. J. Dijkstra, R. J. Sladek

IN earlier work the effect of manganese on the general behavior of nitrogen in iron was the subject of a careful examination by Fast.' Part of the investigation was made, in collaboration with one of the present authors (L.J.D.), by using the internal friction method. This technique, which has been described elsewhere,' showed some significant changes in the properties of Fe-N alloys by the addition of a small amount of manganese namely: 1—Under standard conditions the maximum of the nitrogen peak in pure iron appears around 20 °C and the half width is about 27 °C. By addition of 0.5 atomic pct Mn a general broadening of the internal friction peak occurs. The half width is increased by about 9°C. Moreover, a shift of the maximum of about 5°C toward a higher temperature takes place, Fig. 2. 2—The precipitation of nitrogen from the supersaturated solution, measured, e.g., at 200 °C, was inhibited by the addition of the amount of manganese given in effect 1. The broadening of the nitrogen peak was confirmed in more recent work3 on samples which were prepared from Westinghouse Puron iron. The effect of manganese on the rate of precipitation, however, was much less striking than in the earlier work' based on Philips high purity iron. Theory To explain the first change in properties just referred to, effect 1, the following two assumptions were made:' First, every manganese atom in sub-stitutional solid solution creates around it six interstices located between an iron and a manganese atom, as is evident from Fig. 1. These interstices, conveniently called Fe-Mn interstices, have for nitrogen a free energy level which is AG* lower than the normal Fe-Fe interstices between two iron atoms. For such low concentrations of manganese as 0.5 atomic pct, the possibility that two manganese atoms will be nearest neighbors can be disregarded. Second, it is assumed that in addition to the normal relaxation time TFe at least one new relaxation time, Mn, Fe, enters in the phenomena which is associated with the elementary diffusion jumps between a Fe-Mn interstice and an adjacent Fe-Fe interstice. Fig. 1 gives schematically the free energy for a nitrogen atom as a function of its position along the line ABC. A tentative analysis of the nitrogen peak in a 0.5 pct Fe-Mn alloy based on these assumptions has been made in Fig. 2. The dotted curve with a maximum at 22°C is caused by jumps between Fe-Fe interstices, the dotted curve with maximum at 32°C by jumps between an Fe-Mn and an Fe-Fe interstice. The two effects added together give the dash-dot internal friction curve for the alloy. In the following these two components will be referred to as the normal peak at 22°C and the abnormal one. (The small secondary peak at

Jan 1, 1954